Preparation of dialkenyl sulfides



Patented July 27, 1948 .UNi-TED- STATES PATENT? OFFICE PREPARATION OF nmtnnurt'sptrmns Robert T. Armstrong, Johnson City Tenn; as-

signor to United States Rubber Company, New I I York, N. Y., acorporation of New Jersey V I I No Drawing. Application April 11, 1945,

- Serial No. 587,831

4 Claims. (01. 260-608) invention relates to the method of preparing'sulfides of olefin'hydrocarbons, and to the resultingproducts; I Heretofore it has been necessary to use as starting materials olefinic halides for the preparation of olefin sulfides, and in such cases theyields have beenpoor, An objectof this invention is to use the olefin hydrocarbons directly as a starting materlal with resulting good yields of the sulfides. Further, it has been found that the reaction of olefins, with elemental sulfur, in the absence of zinc or similar metal in combination, produces alkyl alkenyl polysulfides rather than dialkenyl sulfides. By a dialkenyl sulfide is meant a monomeric compound consisting of sulfur bonded to two alkenyl groups. They subscribe tothe formula RSn-R where n is a whole number from 1 to 2, and R is an olefinic radical. I Alkenyl is used in the usual sense to refer to a monovalent I radical containing an ethylenic linkage.

The chemicals are prepared by a method which consists in interacting any olefinic hydrocarbon containing from 3 to 12 prising the group with elemental sulfur, in the presence of zinc or similar metal in combination, and a nitrogencontaining compound which belongs totheclass of rubber vulcanization accelerators.

There should be present at least one molecular proportion of zinc or similar metal in combination for each two molecular proportions of the olefin;

an excesstends to minimize undesirable side reactions. The molecular proportion of the sulfur should be at least 1.5 atomic proportions for each molecular proportion of the olefin. The proportion of the nitrogen-containing accelerator need salt may be added as such or formed in situ, as

where zinc oxide is added with the fatty acid. The reaction for preparing disulfide may be represented by the following equation:

R is an aliphatic radical containing from 3 to 17 carbon atoms.

carbon atoms and comtion,

Examples of olefins are propene, the butenes, the amenes,the hexenes, the heptenes, the catches, the nonenes, the decenes, the undecenes; and the dodecenes. W'here morethan one memher is referred to the intentionis to include each member of the class which contains a hydrogen atom attachedi'to the carbon atom which is alpha tothe double bond.v V 1 [Among the? sulfides may be mentioned 6,6'-dithiobis (5- methyl-4-nonene), and 6,6'-thlobis (5,- methylf-Fi-nonene) Z-butenyl monosulfide and d i-. sulfide, and 2-methyl2-butenyl monosulfideand disulfide. f I Q The sulfides of this invention are clear liquids possessing a persistent garlic-like 'odor and may be used as insecticides, fumigants, and as intermediates in the preparation of dyes, pharmaceuticals, resins, etc. Although the reactive form of the zinc in the reaction appears to be the salt of the organic acids of the fatty acid series, such as zinc propionate, zinc stearate, etc., it is possible to substitute zinc oxide for a portion of the zinc salt only to such extent that the rate of the reaction is not impaired so that undesirable side reactions occur. Also, the salt canbe formed in the reaction by introducing the proper amounts of the zinc oxide and of the acid. I a I In place of zinc, othermembers Of the so-called magnesium-zinc family of elements (see page344 of Mellors Modern Inorganic Chemistry," published by Longman, Green &Company, 1922), which family includes besides zinc, cadmium, magnesium, and mercury-may be used in place of the corresponding zinc compounds. I 1 z-mercaptobenzothiazoleland other thiazylsulfides are exemplary of the so-called vulcanization acceleratorswhich are useful in promoting the reaction of sulfur with olefin according to my invention; others, called thiuram sulfides, such as I tetramethyl thiuram sulfide, tetramethyl thiuramdisulfide, and ureas such as ,diphenyh thiourea, and-amines, ,such as dibenzylamine; diphenylguanidine, and triamylamine, as well as other nitrogen-containing accelerators of rubber vulcanization can be used.

; The re action takes place slowly at room tem-, perature and increases in rate with increasing temperature. The maximum temperature is lim ited only by theteinperature at which thermal decomposition of the products occurs. Eflicient temperatures are in the range from to 180 C. The following xarnples illustrate theinventhe parts being by Weight.

azole, 56 parts of zinc propionate, and 106 parts of zinc oxide is heated for 24 hours at C. The

ing the residue with an acetone-water solution of-- sodium sulfite. The high-boiling;prcdllctdsi.dis; 1

tilled in a molecular still, and is found to consist mainly of a mixture of the.=-dialken-yl ,-disulfides 1 formed by substitution of sulfur at ana-ngethy lene group of the olefin, together with a" small** amount of monosulfide. l v

Analyses Calc. for CzqHaS; s, 10.3;

ExAMrLn: 2 n v A mixture pa ts of trimerihr ethyi '1 90 par so u iu z fidrafisoizim oxi e 85.1w; i. ia lei nate and. zrarts of ZflI QIQ PP bSQWZQT thla ple hsat dat 3. Ci for, 1 1 101 he product, purified as in Example 'labove, is f oun d 9 1 on ist, o nrloximate g e ua .v par f h allsqnyl .mon s lfld and islllvfide which are, hen e ar ed br act smal. di illat on l rider cuum Analyses.-

an olefinic radical, and n is an integer from 1 to 2; which comprises reacting;- at aggt'emperature in the-range frd'mabout 90-"'. to about"'180 C., 2 molecular proportions of an olefinic hydrocarbon containing from 3 to 12 carbon atoms and conwith atleast ljatomic proportions of elemental suljurfln the presence of at least 1 molecular proportionof a metal salt of a saturated fatty acid a; haying irom 3 to 18 carbon atoms, the metal thereof being selected fgrom the magnesium-zinc ami y f me 1 or hem-rio icttablaa ndr cat lystasmmt uheffcctivaamountr ta rcr. gen-containing compound recognizedag; ulcani ati no cc l a rfor: uhban I 3-; A1 me o pre ri g; ial en ll sulfides sub c bin t t for la, Rh us- R an 1efin ad aL and n E an r tcs q rom "1 m w ch mpr s rea t ve z'molec lannmm ionsm anc sfin c hy roca bon; on inin f:

3 t 2 arbonsa om an c t ningltha tructure wi hlatfl eastiiaato ic p o ort ons ,dfvl'e emental ul ur, n th pre ence of .at ast. molecu arln tfla B1B. inlzo" 3 07; Began; r -g g Monosulfide from trimethylethylene: V v

Found Q .fio fifl/fignlmnn 1.497; 0.892. 70.5 1' 1111' 1 18:4 Calc,fo r QmHisS m. 70,6 10.6- 18. 8 Disulfide from t irpethylethylene taco/1mm o. 975 59. 9 9. 4 a1. 7 t 1 594 8.9 31. 7

EXAMPLE:

Butene-2 is reacted withsulfur in a manneranalogous to that of Examples Land 2' above and ithlat ea t 15 t m c l r p rtlon y.oil emental ilv lurr .tha resanccofat1east..1-, 1ac1 1arPm; p rtio f. am a t 1a a rat dl atty. acid ing m 8 1I'p n.. tQ n; e, mt@1.

canization acceleratorfog lrubber.

2. A method of preparing dialkenyl sulfides subscribing tot-then formulalR-asn-rR- where..R,=is

yields a mixture of-the 2-butenylmonoand gdi portion of zinc salt of a saturated fatty acid having from 3 to 18 carbon atomsand as catalysta smallnbut efiective amount of a nitrogen-containing. v compound:::recog1 nized 1 as -a. vulcanization accelerator-i fonrubber. I 4. A method of -preparing dialkenyl sul'fides subscribingcto thaformula *where-R is an olefinic radical, and w isanintegerfrom-1 2 ,1 which (comprises reacting 2--molecular propor tionsof an olefin ic hydrocarboncontaining-from 32to.12 carbonatoms and containing the structure v C=( C m lca izat mo t ubb rt th 1 1- ROBERT ARMSTBQNG REFERENCES 01111511;

T ,I JlQW rsl-m ier nm v. 1.: ozf'reeordim the file of this patent-;:; 3

N TED :ST ES. PAT NTS Number Name Date 2,329,486 Rummelsburg Sept. 14, 1943 2,338,829 Werntz Jan. 11, 1945 

